Polyazo benzidine dyes



Patented Jan. 18, 1949 fir-alo s mrc-.s milioni* torero-E JPQLYAZO BENZIDINEZDYES Fritzv Straub, Kaiseraugst, ,near QseL. andilakb LBrassel, Basel, Switzerland.. assignors2-to-0ba Limited, Basch. Switzerland,";a` Swiss firm 15.Clams.

. l1. :The-...present finventionifs :concerned with. l.dis- '1 and ypolyazo dyestuffsfbf the diaminodiphenyl scories., -ItLfis an object..of..the presentinvention toiprovide/valuablefnew dfyestuffs which .are subs'stantive f :to vcotton and other 4cellulosic `bers. lriviere particularly thafpresent vinvention provides la series oihdyestusfcapablefof--forming complex Ivmetalse'ompo1.1nds,. fonexample, on` after coppering on the ber, and still more particularlyit is an object of the present invention to provide dye'stffsoffitherlsald kind Whichadye `oellu'losic bers red shades of= very good fastnessffto light.

It is well. known in' the art to produce `subsvtantive dyestuffs capable of forming complex metal compounds by uniting tetrazotized 3:3'-diall oxy ll:44'diaminedipheioyls, especially tetrazotized dianlsidinawith coupling components. Although these .dyestufsas a rule, are substantially imfprov'ed by-an .a'fter-coppering on 'the'iber,- the dyeings ,Lthus .obtained y are defective "in several aways. M any.shades, .and inter alia. clearred 4.sl-iaclesf are not. olitainable.with these known dyesstus, and eyfenwthe.ater-coppered dyeings are not :fast to -Washing -4and. 'their-j vfastness; to L light is much impaired by subsequent-,Wettreatments, for example by mild soaping. Therefore there is a strong demand fordye'stufts which are supe- L,rior-.to these known dyestuls. l

ltgh'as now. .beeniound that Valuable .disand fpolyazo: dyestuffs -may be obtained by coupling frtetrazo compounds with.. azo components, .if .necviessary-using further .coupling ,and/.connecting .rel actions: if -tetrazotized -ehydroxy-: 4 -diamino- `:rdiphenyls aroused asJtetrazo compounds, of'wh'ich :one ortho-position to the amino group standing l in',` `iM-position is v'occupied 'by a group incapable W'ofl forming. salts; and if desired-'causing-agents `--"yi"el1ling'metal to'1-eact\with the clyestus fthus obtained.

The v3-hydroxyberizidinesnsed as starting materials vrior .the' present, inventioncontai'n in-l the 5'positionfhydrogen and inthe Sffpo'sition a substituent which is incapable of forming salts such as an alkyl (especially methyl), halogen or preferably an` alkoxy group. Amongst alkoxy groups the .mthoXy group is preferred, but iti is to be understood that other alkoxy groups; such as Tr-vable too. The saidacompoundsare. new.

l The: newI VI-hydroxy-Sf-methoxybenzidine may iibeobta-ined, for examplalfrom 'dianisidine by. parf tial :saponifuzation, tfor. 1 instan-ce,l with. sulphuric i-r-"acidirof'rI moderate :concentra-tion. Thea t.tetrazvozitization r' of these fcompoundsL-mayflbe conductedo: 499,706. In'Switzerland'September'. 2,-'.-1942 y .L2 .ini known manner, ,for example, ina .hydrochloric .acidsolution s l .Thellazo.,corn'ponentsv to.. be united with jthe .tetrazotized ...,3 -hydroxyf -alkoxybenzidnes may 5 l orrinst'ancefbelongto.thebenzene or, naplithalene seriesmpossessma rheterocycliosystem, or contain .the carbonatomapable.-of;.couplng in an Open chain. Therelmay ,be may.. of. example., be. ,mens .tioned `phenols and particularly y salicylic 1 acid, 10.resorcinolpnaphthols, I.n aptl'ithol,ricono anddisultonic acidsffl aminonaphthols. and- -their 4su'lfonc aoidstasewellas other components, normally,` used mfom thefmanufacture oLazo dye'stuis. .1 Further- ..morentherelcomelinto.consideration..particularly 15 also 'pyrazolones.whihsmay be substituted in knoyvnirnanner fior: example by-lanlaryl 4radical in .Agpositioni and: by af, ,methyl Cor carboxyl. group in fak-position. ,-.-[n,-:this-ca`se .also thearyl nucleus. lforfexarppleethe benzene..nucleus,v may carry. sub- 20,stituents.=suclr Aasgfor .earaxicplev a4 sulfarnide, group, a aanitro-.oixamino group-as Well. asthe salicylic. acid -grouping Asl-:open ,chain .azo components. there neome-lforiinstance Linto..consideration` acetoacetic aacidlarylides. 25 For.lcouplng.,wth :theietrazotized lS-hyclro'xy- 3'.s=alkoxyhenzidines f; 2 molecular `proportions of i .the same-, or,v different. .coupling .components may .,llloe'used. .Iffdisazodyestuffs are, aimed at,.coupling c .components-l .arer'fused which 4do ynot contain azo 3Q;.gro ups. Particularly -`Valuable. ,vdyestuifs are in z,lmanyf-cases,obtainedy if, as azo components. at least f onemyrazolonesis fused; .and/on such 4con'lponents Whchifoontain the-salicylic. acid grouping. Both f1characteristicsmaw-simultaneously be present .in

.4oithe,,present.;inyention. For the, production of r.strisazo..,anctpolyazo.-hlyestufs use `,may be, made withadvantagea-onazo.,icnmponents ,which .con- .-tai1:ll..anY ,amino ,group capable of further diazotization or a radical convertible into su'ch an amino .,ponents A.which 1lare. l'aimable -of .rep eated coupling, lorsalso .isuch .components which. lend, themselves to otherbonnectng reationsgleading to thesyn- 50..,tion; reductive.'connectioniof twonitro groups,

may then be converted in known manner into trisazo or polyazo dyestuffs. Furthermore trisand polyazo dyestuffs can be obtained by using monoand polyazo dyestuis capable of coupling as coupling components either on one side only or on both sides.

Since in the tetrazotized 3hydroxy4:4diaminodiphenyls whose 3-pcsition is occupied by a substituent free from salt forming properties the 4diazo group possesses a greater coupling energy than the l-diazo group, it is well possible and in many instances preferable to unite the said tetrazo compounds successively with two diierent coupling components. In this case it may be of advantage to couple the said tetrazo compound irst with a coupling component which is capable of forming complex metal compounds by itself, i. e. without the aid of the azo group attached to the diaminodiphenyl component.

This condition is fulll'ed for example with salicylic acid, or coupling components containingl the salicylic acid group or an ortho-ortho'-dihydroxy azo grouping or an lortho-hydroxy-ortho-carsolution of about percent strength until a very weakly alkaline reaction occurs. A mixture of 3-hydroxy-3'-methoxybenzidine and 3:3'di hydrc-xybenzidine separates. This mixture is ltered, washed with Water and dried. From the dried base mixture the 3hydroxy-3methoxy benzidine may be extracted with chlorobenzene at 100 C. By repeated recrystallization from benzene 3-hydroxy-3methoxybenzidine of melting point 153-154" C. is obtained.

The following examples illustrate the invention, the parts being by weight unless otherwise stated:

vExample 1 2.3 parts of 3-hydroxy-3-methoxybenzidine are dissolved in 5 parts by Volume of hydro- Y chloric acid oi' 30 percent strength and 100 parts boxy grouping, etc'.` As Vsecond coupling components those are preferred which allow coupling in ortho position to ,a hydroxyl group thus leading to an ortho-ortho'dihydroxy grouping, with the hydroxyl group ofthe tetrazo component.

The dyestus obtained according to the present invention are suitablefory dyeing and printing the most various animal and particularly cellulosic bers such as wool, silk, lcather'and especially cotton, linen, rayon and staple ber from regenerated cellulose. Amongst others Very valuable red shades are also obtained.

Favorable results are obtained if agents yielding metal, particularly agents yielding -copper are caused to react on the dyestuis obtained which reaction may be performed in substancafinthe dyeing bath, or on the fiber. instance due to the presence `of 'two or more groups lending solubilityto the dyestus, particularly sulfonic acid groups, is-constituted inl such a manner that its complex metal compoundsY produced in substance, for instance complex after-coppering process or more simply accordingto the dyeing process known for example from the U. S. Patent 2,148,659 (see also French Patent No. 809,893), according toA which dyeing is conducted in the same bath as the after-treatment with agents yielding metal, particularly agents yielding copper. Such agents yielding copper mainly come into consideration which are stable towards alkalies, such vas complex copper tartrates.

3-hydroxy-3-methoxybenzidine used in the following examples can be produced as follows:

560 parts of sulfuric acid of 65 percent strength are heated to 135 C. and then introduced into 125 parts oi dia-nisidine. Whilst stirring and cooling in the reflux apparatus the mixture is heated during about 36 hours to the boil (140 0.). The

.whole is then allowed to cool to about C.

whilst stirring and the precipitate obtained ltered ofi. The residue is suspended in '400 parts of water and mixed'at'fl7 C. with a caustic soda of water, and tetrazotized at 5 to 10 C. with 20 parts of a n-sodium nitrite solution. The tetrazo compound is added to a solution of 1.7 parts of salicylic acid and 6 parts of sodium carbonate in 50 parts of Water and stirred for one hour at 5 to 10 C. The reaction mixture is then mixed with asolution of 2.55 parts of 1(3' sulfamidophenyl)-S-methyl-5-pyrazolone and 2 parts of sodium carbonate in 50 parts of Water and the whole is-stirred for hours at 20 to 25 C. The dyestui thus obtained of the probable formula v Holi l sozNHi is then separated in `the heat by addition of sodium chloride and filtered off. It is a dark powder, which dissolves in water and dilute alkalies to a brown-red and in concentrated sulfuric acid to a ruby-red solution. The dyestuil dyes cotton red shades which are fast to washing on being dyed and coppered according to the one bath process.

Example 2 OS OQNHI is filtered off, washed with a solution of sodium chloride 'of 10 percent strength, and then dried. It forms a dark powder, which dissolves in Water and sodium carbonate solution to a brown-red, in dilute caustic alkalies to an orange and in concentrated sulfuric acid to a ruby-red solution. The dyestuff dyes cotton red shades which are S OzNHa ciutat-46a mi ya hour at e #of Gf. ci .Meri this time theL monoazo-r dyestu is; formed; A lsolution i of 5.85 parts i- 1.1ilfhydrewfffarboxyphenrl)=3ff metb-.rlv-Pillazqloee and zffnartseof so'diwn hy.- drexde. in; .Smarts-1f of .water are added ,to the Geuplns mixture .This mixture is.v stirred; for- .1. hour: at10.fto:1123C-. and.7then..fo 20 khours ati 15 con to 20. Bye-duiden "ef sddiiilif chlidgthefdyestuff thus obtained of the probableformula is-fseparatedr" When@ dryitfforms-i 'a :green-black bronzyi powderiswhich dissolves: in' 'Water tocan pyrazolone.

uuic-"paris5 #munitiSfrrieuuxybenzidue ,eretefrazstissd withrsedlium .nitrite-.m theusuail maunerjfand in'',tliebresenc:e.o fv4 hydrochloric acid. The clear' solution ci. the4 #trazo compounduis umted fwithfwsomuon erede-pares orsaiic'yne acid and 6 parts of sodium hydroxideinlio'fparts of water at 5 C. Theyholeis stird'fory to 1 hour at 4 to 6 Quafsolutoriof 4.73-parts`of 1 (3aminophenyl) -3laiietl 1v1-5mprazolopeg:4 and 2 parts of sodium-. hydrxidein parts of water is added and stirring is continued for 1 hour at 6 lof 'tlzg cf: andttnenrfor 2o 'tot 25y hours att/151:0 "Ca l Afteftheneutralizauonwith hydrochloric acidth'e d'is'azo' iy1e'stulisI filtered-off and dis"-` solved by addition#of2"?parts;of sodium hydroxidein 400 parts of water at 50 C. 25 parts by volume of a N-sodium nitrite solution are adde'd tothe dyestuiisolution.- After additionl of 10Q partsof ice 65'v parts-lof 2N-hyolro'clnloric'l acid* are introduced. After hours surfing at 1o to;15 o. me diazot'ization is complete. The diazo-disaaovdyestuff is separated by addition of sodium chloride and added as a moist paste to a solution of 5185 parts of 1.-(4'ehydroxyf-3'-carboxyphenyl) '-133 n'letliy"4 pff/ra'zolori'e"I and; 6 parts oi" sodium hydroxide in 9i) parts of Water. The Whole is' stirred for one hour at 1G to 12 C; and coupling' is completed at 18 to 20C; The trisazo dyestuff thus obtained of the formula Example' 5 2.3 `parts Vof B-hydroxy-B-methoxybenzidine are dissolvedin 5 parts by volume of hydrochloric acid of percent strength and 100 parts of Water, and tetrazotized at 5 to 10 C. with 20 parts by Volume of sodium nitrite solution. The tetraZo-compound is added to a vsolution of'4,8 parts of'1-amino-8-naphthol-4-sulfonic acid, 6 Iparts of sodium chloridehand 2parts of` caustic sovdafsolution of Solpeitcent strength lin parts of`,water.v fIhe reaction mixture is stirred for couleurs-ams ,tu zogcganlthe dyestuff separated byjadditioriofj sodium chloride. After drying it f dlrrus'4 aidarli p ovyde` which dissolves in' Water and soclium..carbonate'solution tofa pure blue,

acetate?.

i in dilute caustic alkalies to a Violet blue, in dilute acetic acid to a violet and in concentrated sulfuric acid to a greenish blue solution. The dyestuff thus obtained of the probableformula HlN H I no ring .ea-@Q m.

K CH3 Y. H

Sl 0 3H O 3H dyes cotton blue shades, which are fast to Washing on being dyed and coppered according to the one bath process.

Example 6 4.6 parts of 3-hydroxy-B-methoxybenzidine are tetrazotized with sodium nitrite in the usual manner and in presence of hydrochloric acid. The tetrazo solution is 'united with a mixture of 18.44 parts of 5.5dihydroXy-2.2-dinaphthylamino-7 7'disulfonic acid and 20 parts of calcined hydroxide in 50 parts of Water at 5 C. The Whole is stirred for one hour at to 8 C. for 16 hours at 18 to 20 and the coupling is completed at to 30 C. After addition of 30 parts of sodium carbonate and 400 parts of water the coupling mixture is heated for some time to 50 C. The Whole is filtered off from the precipitated calcium carbonate and the dyestui is isolated by addition of sodium chloride and hydrochloric acid. When dry it forms a dark green-bronzy powder of the probable formula noaa-@NH- oH n o o H3 which dissolves in water and dilute alkalies toa cornflower blue and in concentrated sulfuric acid to a greenish blue solution and dyes Vegetable fibers blue shades which are fast to washing on being after-treated with coppercompounds.

Example 7 l 5.75 parts of 3-hydroXy-3-methoxybenzidine are tetrazotized with sodium. nitrite in the usual manner and in presence of hydrochloric acid. i

which dissolves in Water to a brown-red, in dilute soda solution to an orange-brown, in dilute caustic alkalies to an orange and in concentrated sulfuric acid to a fuchsine-red solutionv and dyes vegetable fibers bordeaux-red shades which are very fast to Washing Iand light on being dyed and coppered according to the one bath process.

5.75 parts of 3hydroxyf3fmethoxybenzidin are tetrazotized with sodiumrnitrite in the usual manner and in presence of hydrochloric acid. The clear solution of' the* tetrazo` compound is added at 10-15'C'.1'to a solution alkalinewith sodium carbonate of 7.73 parts ofthe dyestuff prepared vloy-fcoupling l molecular proportion oi.' diazotized Z-"amino-1=pheno14sulfamide with 1 molecular proportion of resorcinolin a, medium alkalinevi'vith sodium carbonate. The whole is stirred for lfhour'atlo to 12- C. and a causticalkaline solution of v5.85parts of 1(4hydroxy 3'carboxyphenyl) 3-methy1-5-pyrazo1one is then added to the 'coupling 'mixture The Whole is again stirred for 1 hour atjl5`to 18 andfthe coupling is completed by heating to 35 to 40 for 20 to 30 hours. The -trisazo dyestuff is separatedV by addition oi sodium chloride and hydrochloric acid. -When dry it is 4a green powder of bronze lustre of the probable formula COOH 100 parts of cotton are introduced at 50 C. into a dye-bathcontaining inl 2500 parts of Water 2 parts of sodium carbonateand 1.5 parts of the dyestuf preparedV accordingto Example 3, rst paragraph, andthe temperature is; slowly raised to -95C. 30 parts of Glaubers salt are added after 1AL-.hour andfdyeing is continued at-this temperature for a further hour. The .bath is then cooled to about 70"I Csfthe necessary quantity of a solution of complex copper tartrate made reebIy alkaline with' 'sodium' carbonate 'isfadded and the' Imaterial is coppe'redatSO-QO" C. for 1/2 hour. It isfth'oroughly'rinsed 'and soaped for a short time,if necessary'. The lcotton isdyed lfast red tints.'

AWhat We claim is: f f

l. A dyestuif of the formula 1:9 wherein: R1. andlRc vstanclfor radicals. of coupling components selected from the class consisting .of couplingcomponents of the benzene, naphthalene and pyrazoloneseries, :c stands for an alkoxy group, and R2 contains a hydroxyl group in a t position viciral to thev azog-rup. i 2. `A dyestuff, lof the formula Clo n OH wherinRi and R2 stand for radicals of coupling `components `selected fromlthe class consisting of coupling components of tliegbenzene, ynaphtha- `Iene E.and pyrazolone series, and R2 contains a K Q-hydroxyl group ina position vicina] to the azo group.

" A dyestuff of the formula `irqllieieiii-Ri anduRz standvfcr different radicaIs of coupling components selected from the class consisting of' coupung components cf the-benzene, naphthalene and pyrazolone series, and R2 contains a hydroxyl group in a position wicinal to the azo group.

4. A dyestui of the formula wherein Ri stands for a radical of a hydroxylcontaining coupling component selected from the class consisting of coupling components of the benzene, naphthalene and pyrazolone series which is capable of forming complex metal compounds by itself and Rz stands for a radical of a hydroxylcontaining coupling component selected from the class consisting of coupling components of the benzene, naphthalene and pyrazolone series which is .bound to the azo group in a position vicinal to a hydroxyl group.

6. Ag-dyestui ofthe for-mula kwherein R1 stands-for, a radical of a salicylic acid and R2 stands for a pyrazolone coupling component.

7. A dyestuffof the-formula CIOOH CH3 Wheitein R2 stands fora pyraz'olonev coupling com- `ponent.

-8. A dyestui. ofthe formula WhereinRi stands for-the radicalof a monoazo dye-stuff capable 'oicouplfing and capable of forming complex metal compounds, said monoaz'o dye- Stuff being built up from components selected from thebenzene,naplitllalt-inev and lpyratzolone series, and R2 stands for a pyrazolone coupling component.

9. A dyestuff of the formula C O O H C H3 O H wherein R2 stands for a pyrazolone coupling component containing at least one azo group.

l0. The dyestui of the formula 11. The dyestui of the formula HO-O oon ons n \N/N 5. A dyestuff of the formula OH; H

wherein R1 stands for a radical of a coupling component selected from the class consisting of coupling components of the benzene, naphthalene and pyrazolone series and capable of forming complex metal compounds by itself and R2 stands for a pyrazolone coupling component.

13. Process for the manufacture of a dyestui containing at least two azo groups, comprising coupling a tetrazotized 3-hydroxy3methoxy 4:4diaminodiphenyl first with one molecular proportion of salicylic acid and afterwards with one molecular proportion of l-(3'sulfamidos phenyl) -3-rnethy1-5-pyrazolone- 14. Process for the manufacture o a trsazo dyestui, comprising coupling tetrazotized 3-hydroxy-S -metlioXy-4 1 4 -diaminodiphenyl rst with one molecular :proportion of salicylic acid, then With one molecular proportion of 1-(3' aminophenyl)-3methy15pyrazolone, diazotizing the amino-disazo dyestuff thus obtained and coupling the diazo compound with one molecular proportion of 1-(4-hydroXy-S'-carboxyphenyD 3-methy1-5-pyrazolone.

15. Process for the manufacture of a trisazo dyestui, comprising coupling tetrazotized S-hydroxy-S -methoxy-4 2 4' -diaminodiplienyl rst with one molecular proportion of the monoazo dyestuff from diazotized 2-amino-1-hydroxybenzene-ll-sulfamide and resorcinol and afterwards with one molecular proportion of 144-` REFERENCES CITED The following references are of reco-rd in the .ille of this patent:

UNITED STATES PATENTS Number Name n Date 412,148 Williams Oct. 1, 1889 1,210,751 kAnderwert et al Jan. 2, 1917 1,792,355 Boeniger Feb. 10, 1931 1,889,732 Stusser et al Nov. 29, 1932 1,995,902 Scheurer et al Mar. 26,` 1935 2,193,438 Taube et al Mar. 12, 1940 2,241,796 Taube et al May 13, 1941 FOREIGN PATENTS Number Country Date 13,235 Great Britain June 27, 1891 18,020 Braat Britain June 26, 1896 102,881

Great Britain Jan. 4, 1917 Certificate of Correction Patent No. 2,459,467. January 18, 1949 FRITZ STRAUB ET AL.

It is hereby certified that error appears in the printed specification of the above. numbered patent requiring correction as follows:

Columns 9 and 10, claim 11, in the formula, rightehand portion thereof, for

en. p CCH` Ill read IQI and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case n the Patent Office.

Signed and sealed this 7th day of June, A. D. 1949.

[IML] THOMAS F. MURPHY,

Assistant O'ommz'ssz'oner of Patents.

Certificate of Correction Patent No. 2,459,467. January 18, 1949 FRITZ STRAUB ET AL.

It is hereby certified that error appears in the printed specification of the above. numbered patent requiring correction as follows:

Columns 9 and 10, claim 11, in the formula, rightehand portion thereof, for

en. p CCH` Ill read IQI and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case n the Patent Office.

Signed and sealed this 7th day of June, A. D. 1949.

[IML] THOMAS F. MURPHY,

Assistant O'ommz'ssz'oner of Patents.

Certificate of Correction Patent No. 2,459,467. January 18, 1949 FRITZ STRAUB ET AL.

It is hereby certified that error appears in the printed specification of the above. numbered patent requiring correction as follows:

Columns 9 and l0, claim 11, in the formula, right-hand portion thereof, for

CHI C-CHI It read Il, and that the said Letters Patent should be read With this correction therein that the same may conform to the record of the ease in the Patent Office.

Signed and sealed this 7th day of June, A. D. 1949.

[IML] THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

